CN107946647A - Electrolyte for lithium secondary battery and the lithium secondary battery including it - Google Patents

Electrolyte for lithium secondary battery and the lithium secondary battery including it Download PDF

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Publication number
CN107946647A
CN107946647A CN201711283431.3A CN201711283431A CN107946647A CN 107946647 A CN107946647 A CN 107946647A CN 201711283431 A CN201711283431 A CN 201711283431A CN 107946647 A CN107946647 A CN 107946647A
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Prior art keywords
secondary battery
lithium secondary
electrolyte
additive
lithium
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姜润锡
朴珉植
文晙荣
朴晋焕
李东埈
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Samsung Electronics Co Ltd
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Samsung Electronics Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to the electrolyte for lithium secondary battery and the lithium secondary battery for including it.For the electrolyte of lithium secondary battery, the electrolyte includes lithium salts, non-aqueous organic solvent and the additive represented by following formula 1, wherein A1‑A9, CY1 and CY2 it is identical with defined in specification.

Description

Electrolyte for lithium secondary battery and the lithium secondary battery including it
The application is Chinese invention application (denomination of invention：Electrolyte for lithium secondary battery and the lithium including it are secondary Battery, the applying date：On September 21st, 2012；Application number：201210356766.4) divisional application.
Cross reference to related applications
This application claims the korean patent application No.10-2011- submitted in Korean Intellectual Property Office on the 22nd of September in 2011 0095812 rights and interests, the disclosure of which are all introduced herein by quoting.
Technical field
Present disclosure is related to the electrolyte for lithium secondary battery and the lithium secondary battery including it, and more specifically, It is related to the life characteristics at high temperature for improving battery and the electrolyte for lithium secondary battery and the lithium including it of High temperature storage characteristic Secondary cell.
Background technology
Lithium secondary battery can be recharged with high-speed, and be had for existing lead accumulator, nickel-cadmium cell, nickel-hydrogen The energy density of the high per unit weight of at least three times of battery or nickel-zinc cell.In addition, the rate of charge of lithium secondary battery is High.Due to such feature, the research and development of lithium secondary battery is actively carried out.
In general, lithium secondary battery includes cathode, anode and the partition plate being arranged between the cathode and anode and electrolysis Matter.Especially, it is secondary to improve lithium without largely effecting on the physical property of electrolyte by adding a small amount of additive to electrolyte The method of the performance of battery causes many attentions.
Additive agent electrolyte has multiple functions.For example, the additive can be formed for prevent electrode active material and The solid electrolyte interface (SEI) directly contacted between electrolyte.Additive for forming SEI on the surface of electrode can It is divided into and is used to help the cathode additive agent that SEI is formed on the surface of graphite and the mistake for forming thick film on the surface of cathode Charge protection (OCP) additive.
With for the lithium secondary battery with high-energy-density for example for electric car battery recent increase in demand, Carry out to high-voltage anode active matter Quality Research.But not yet implement to for preventing at positive active material surface The research of the additive agent electrolyte of the oxidation of the electrolyte of generation.
In general, the potential window of electrolyte need it is wider than the potential difference between positive active material and negative electrode active material. But with using for high-tension active material, to increase the energy density of battery, the potential window of electrolyte has become It is narrower than the potential difference between positive active material and negative electrode active material.Therefore, can be used to prevent electrolyte and electricity by being formed The film directly contacted between the active material of pole and prevent the decomposition of electrolyte.
If using aromatic compounds such as biphenyl and terphenyl as additive agent electrolyte, the additive agent electrolyte passes through When the voltage of battery is equal to or higher than reference voltage value at the surface of cathode formed thick film with stop lithium ion by with Electric current flowing and play the role of OCP.Recently, it has been suggested that formed by using the additive of low concentration at the surface of cathode thin The method of film.But the battery behavior of acquisition is not gratifying, and therefore still suffer from many improved spaces.
The content of the invention
The electrolyte for lithium secondary battery is provided, wherein preventing its oxidation at the surface of cathode with it in cathode Polarity film is formed in surface portion, thus promotes the migration of lithium ion.
Lithium secondary battery with excellent life characteristics at high temperature and High temperature storage characteristic is provided.
In addition aspect will be illustrated partly in the following description, and partly will be apparent from the description, or can lead to The practice for crossing provided embodiment is learned.
According to an aspect of the present invention, the electrolyte for lithium secondary battery includes lithium salts, non-aqueous organic solvent and under The additive that formula 1 represents：
<Formula 1>
Wherein A1-A9It is each independentlyCondition is A1-A9Bag IncludeIt is at least one；
CY1 is C3-C6 aromatic rings, and CY2 is C2-C5 aromatics or non-aromatic ring；
B1And B2Be each independently singly-bound,Or C1-C5 alkylidenes；With
R1And R2It is each independently hydrogen, halogen group, cyano group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa,-S (=O) Ra,-S (=O)2Ra、-P(Ra)2, substituted or unsubstituted C1-C20 alkyl, substitution or Unsubstituted C1-C20 alkoxies, substituted or unsubstituted C2-C20 alkenyls, substituted or unsubstituted C2-C20 alkynyls, C2-C20 It is oxyalkylene group, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryls or its combination, wherein RaFor hydrogen, C1-C10 alkyl or C6- C20 aryl,
Condition is R1And R2It is at least one including polar functional group chosen from the followings：Halogen group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa、-P(Ra)2, substituted or unsubstituted C1-C20 alkoxies, C2-C20 oxyalkylene groups, substituted or unsubstituted C6-C30 aryloxy group and substituted or unsubstituted C2-C30 heteroaryls.
The additive can be represented by following formula 2：
<Formula 2>
Wherein A1And A2It is each independentlyCondition is A1With A2IncludingIt is at least one；
B3And B4Be each independently singly-bound,Or C1-C5 alkylidenes；With
R’1、R’2、R”1、R”2、R”3And R "4It is each independently hydrogen, halogen group, hydroxyl, cyano group ,-C (=O) Ra、-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa,-S (=O) Ra,-S (=O)2Ra、-P(Ra)2, it is substituted or unsubstituted It is C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxies, substituted or unsubstituted C2-C20 alkenyls, substituted or unsubstituted C2-C20 alkynyls, C2-C20 oxyalkylene groups, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 virtues Base, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryls or its combination, wherein RaFor hydrogen, C1-C10 alkyl or C6-C20 aryl,
Condition is R '1、R’2、R”1、R”2、R”3And R "4It is at least one including polar functional group chosen from the followings：Halogen radical Group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa、-P(Ra)2, it is substituted or unsubstituted C1-C20 alkoxies, C2-C20 oxyalkylene groups, substituted or unsubstituted C6-C30 aryloxy group and substituted or unsubstituted C2- C30 heteroaryls.
The additive can be at least one chosen from the followings：
The amount of the additive can be in the range of about 10 weight % of about 0.005-, the gross weight based on the electrolyte.
The lithium salts can be one kind chosen from the followings：LiPF6、LiBF4、LiSbF6、LiAsF6、LiCF3SO3、Li (CF3SO2)3C、Li(CF3SO2)2N、LiC4F9SO3、LiClO4、LiAlO2、LiAlCl4、LiBPh4, wherein x and y be natural number LiN(CxF2x+1SO2)(CyF2y+1SO2), LiCl, LiI, di-oxalate lithium borate (LIBOB), and combinations thereof.
The non-aqueous organic solvent may be based on (carbonates) solvent of carbonic ester, (esters) solvent, base based on ester (ethers) solvent in ether, (ketone) solvent based on ketone, (alcohols) solvent based on alcohol, aprotic solvent or its combination.
According to another aspect of the present invention, lithium secondary battery includes：Cathode, it is wherein or de- from it includes Lithium-ion embeding Embedding positive active material；Anode, it includes Lithium-ion embeding wherein or the negative electrode active material from its deintercalation；And between institute The electrolyte between cathode and anode is stated, wherein the electrolyte includes lithium salts, non-aqueous organic solvent and added by what following formula 1 represented Add agent：
<Formula 1>
Wherein A1-A9It is each independentlyCondition is A1-A9Bag IncludeIt is at least one；
CY1 is C3-C6 aromatic rings, and CY2 is C2-C5 aromatics or non-aromatic ring；
B1And B2Be each independently singly-bound,Or C1-C5 alkylidenes；With
R1And R2It is each independently hydrogen, halogen group, cyano group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa,-S (=O) Ra,-S (=O)2Ra、-P(Ra)2, substituted or unsubstituted C1-C20 alkyl, substitution or Unsubstituted C1-C20 alkoxies, substituted or unsubstituted C2-C20 alkenyls, substituted or unsubstituted C2-C20 alkynyls, C2-C20 It is oxyalkylene group, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryls or its combination, wherein RaFor hydrogen, C1-C10 alkyl or C6- C20 aryl,
Condition is R1And R2It is at least one including polar functional group chosen from the followings：Halogen group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa、-P(Ra)2, substituted or unsubstituted C1-C20 alkoxies, C2-C20 oxyalkylene groups, substituted or unsubstituted C6-C30 aryloxy group and substituted or unsubstituted C2-C30 heteroaryls.
The cathode includes forming film in its surface, wherein the membrane part or fully deriving from the electrolyte In the additive.
The thickness of the film can be in the range of about 0.5nm- about 100nm.
The amount of the additive can be in the range of about 10 weight % of about 0.005-, the gross weight based on the electrolyte.
The positive active material can be at least one chosen from the followings：LiCoO2, wherein 0≤x<1 LiNi1-xCoxO2, Wherein M is Mn or Fe and 0.03<x<0.1 Li1-xMxO2, wherein 0<x<0.5 Li [NixCo1-2xMnx]O2, wherein 0<x≤0.5 Li [NixMnx]O2, wherein 0<x≤1、0≤y<1st, 2≤z≤4 and the Li that M is transition metal1+x(M)1-yOz, wherein M for Ti, V, or Mn LiM2O4, wherein M is transition metal and 0<The LiM of x≤1xMn2-xO4, LiFePO4, wherein M is Mn, Co or Ni LiMPO4, V2O5, V2O3, VO2(B), V6O13, V4O9, V3O7, Ag2V4O11, AgVO3, LiV3O5, wherein 0<δ-the Mn of y≤1yV2O5, δ-NH4V4O10, Mn0.8V7O16, LiV3O8, wherein 0<The Cu of x≤1xV2O5, wherein 0<The Cr of x≤1xV6O13, wherein M is transition gold Category and the M that X is S, P, As, Mo or W2(XO4)3, and the Li that wherein M is Fe, V or Ti3M2(PO4)3。
The positive active material can have the operating potential of 4.5V ± 0.5V.
Brief description of the drawings
By being described below for the embodiment that is considered in conjunction with the accompanying, these and/or other side will be apparent and more hold It is readily understood, wherein：
Fig. 1 is illustrated when the additive for lithium secondary battery of embodiment according to the present invention is added in electrolyte The schematic diagram of solid electrolyte interface (SEI) film formed at the surface of cathode；
Fig. 2 is shown in be used to be melted into according to embodiment and the lithium secondary battery of electrolyte experience that includes of comparative example preparation (formation) be charged and discharged twice and then reference charging disassembles once and the X-ray photoelectron of the film of post analysis The figure of spectroscopy (XPS) result；
Fig. 3 is the decomposition diagram of the lithium secondary battery of embodiment according to the present invention；
Fig. 4 A are the figures shown according to the lithium secondary battery that embodiment and comparative example manufacture in 45 DEG C of life characteristics at high temperature；
Fig. 4 B are the figures shown according to the lithium secondary battery that embodiment and comparative example manufacture in 60 DEG C of life characteristics at high temperature；
Fig. 5 is shown in the appearance of lithium secondary battery lithium secondary battery after 100 DEG C of placements of embodiment and comparative example Measure the figure of conservation rate；
Fig. 6 be shown in embodiment and comparative example lithium secondary battery place at 100 DEG C after the lithium secondary battery open The figure of road voltage (OCV) drop；With
Fig. 7 is shown in the appearance of lithium secondary battery lithium secondary battery after 100 DEG C of placements of embodiment and comparative example Measure the figure of recovery rate.
Embodiment
It will be described in detail embodiment now, the example illustrates in the accompanying drawings, wherein identical reference numeral refers to all the time Identical element.At this point, present embodiment can have different forms and should not be construed as limited by set forth herein Description.Therefore, embodiment is described solely by reference to attached drawing below, to explain each side of this description.As used herein Term "and/or" include one or more any and all combinations of related Listed Items.Statement for example " ... at least one Kind (a) " modifies whole key element list and does not modify the independent key element of the list when before or after key element list.
Hereinafter, will be described in for the electrolyte of lithium secondary battery and including the lithium secondary battery of electrolyte One or more embodiments.But these embodiments are merely provided for the purpose of explanation, and it is not intended to limit the present invention's Scope.
According to the embodiment of the present invention, for lithium secondary battery electrolyte include lithium salts, non-aqueous organic solvent and by The additive that following formula 1 represents：
<Formula 1>
Wherein A1-A9It is each independentlyCondition is A1-A9Bag IncludeIt is at least one；
CY1 is C3-C6 aromatic rings, and CY2 is C2-C5 aromatics or non-aromatic ring；
B1And B2Be each independently singly-bound,Or C1-C5 alkylidenes；With
R1And R2It is each independently hydrogen, halogen group, cyano group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa,-S (=O) Ra,-S (=O)2Ra、-P(Ra)2, substituted or unsubstituted C1-C20 alkyl, substitution or Unsubstituted C1-C20 alkoxies, substituted or unsubstituted C2-C20 alkenyls, substituted or unsubstituted C2-C20 alkynyls, C2-C20 It is oxyalkylene group, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryls or its combination, wherein RaFor hydrogen, C1-C10 alkyl or C6- C20 aryl,
Condition is R1And R2It is at least one including polar functional group chosen from the followings：Halogen group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa、-P(Ra)2, substituted or unsubstituted C1-C20 alkoxies, C2-C20 oxyalkylene groups, substituted or unsubstituted C6-C30 aryloxy group and substituted or unsubstituted C2-C30 heteroaryls.
The additive of the formula 1 can be (benzazoles, the benzazole- based on benzothiazole with polar functional group Based) compound or derivatives thereof.The example of the compound based on benzothiazole includes (indazole class) chemical combination based on indazole Thing, (benzimidazole) compound based on benzimidazole and (benzotriazole) compound based on benzotriazole.
Before the non-aqueous organic solvent is by oxidation, the additive of the formula 1 is aoxidized, because it is with more non-than described The low oxidation potential of aqueous organic solvent, thus forms film on the surface of cathode.It is therefore possible to prevent powered on the surface of the cathode Solve the oxidation of matter.
Managed when using polarizable continuum Model (polarizable continuum model, PCM) and Density functional Calculating is for example used for by Gaussian03 codes and 6-311+G (d, p) base group by B3LY to calculate the additive of the formula 1 During oxidation potential, existed by showing the oxidation potential of additive of the formula 1 than the low about 2V susceptible of proof of the non-aqueous organic solvent By before oxidation, the additive of the formula 1 is aoxidized the non-aqueous organic solvent.
In addition, the additive of the formula 1 includes the polar functional group with non-covalent electron pair for possessing electron donation With the nitrogen-atoms with non-covalent electron pair in heterocycle, and therefore have possess reduction oxidation potential core part, thus Form film.Moreover, the additive of the formula 1 can provide for smoothly migrating the passage of the lithium ion of the electrolyte, by This can obtain the lithium secondary battery with improved life characteristic.
Fig. 1 is illustrated when the additive for lithium secondary battery according to embodiment is added in electrolyte in cathode Surface portion on form the schematic diagrames of SEI films 26.
With reference to figure 1, when using the additive of the electrolyte for lithium secondary battery, the SEI films of thin and firm (solid) 26 are formed in the surface portion as cathode on the surface of positive active material 22, and therefore lithium ion 24 is effectively moved from cathode Move on to electrolyte 28.
Specifically, the additive of the formula 1 includes possessing the polar functional with non-covalent electron pair of electron donation Group and the nitrogen-atoms with non-covalent electron pair in heterocycle, and therefore polymer is formed with non-aqueous organic solvent.Therefore, exist On positive active material 22 formed lithium-ion-conducting SEI films 26, and provide be used for more smoothly migrate electrolyte lithium from The passage of son, it refers to Fig. 2 confirmations.
It is formed in the film on positive electrode surface and suppresses other electrolyte side reaction and the elution of metal ion, or even Battery is also in this way, thus contributing improved High temperature storage characteristic and life characteristic when being exposed to high temperature.
The definition of term " substituent (substituted group) " in formula 1 is described below.
Herein in connection with above group alkyl, alkoxy, alkenyl, alkynyl, oxyalkylene, cycloalkyl, aryl, the virtue in formula 1 The term " substitution " that epoxide and heteroaryl use refers to following substitution：Halogen atom, the C1-C20 alkane substituted with halogen atom Base (such as CF3、CHF2、CH2F、CCl3Deng), hydroxyl, nitro, cyano group, amino, amidino groups, diazanyl, hydrazone group, carboxyl or its salt, sulphur Acidic group or its salt, phosphate or its salt, C1-C20 alkyl, C2-C20 alkenyls, C2-C20 alkynyls, C1-C20 miscellaneous alkyls, C6-C20 Aryl, C7-C20 aralkyl, C2-C20 heteroaryls or C3-C20 heteroarylalkyls.
The example of C1-C20 alkyl used herein include methyl, ethyl, propyl group, isobutyl group, sec-butyl, the tert-butyl group, Neopentyl, isopentyl and hexyl.At this point, at least one hydrogen atom of the alkyl can use and on terms above " substitution " The identical substituent limited replaces.
The example of C1-C20 alkoxies used herein includes methoxyl group, ethyoxyl and propoxyl group.At this point, it is described At least one hydrogen atom of alkoxy can use to be replaced with the identical substituent that terms above " substitution " limits.
The example of C2-C20 alkenyls used herein includes vinyl and pi-allyl.At this point, the alkenyl is extremely A few hydrogen atom can use to be replaced with the identical substituent that terms above " substitution " limits.
C2-C20 alkynyls used herein can be such as acetenyl.At this point, at least one hydrogen of the alkynyl is former Son is available to be replaced with the identical substituent that terms above " substitution " limits.
The example of C2-C20 oxyalkylene groups used herein includes ethylene oxide, propylene oxide and butylene oxide base Group.
The example of C3-C30 cycloalkyl used herein includes cyclopropyl, cyclobutyl, cyclopenta and cyclohexyl.This point On, at least one hydrogen atom of the cycloalkyl can use to be replaced with the identical substituent that terms above " substitution " limits.
C6-C30 aryl used herein can refer to the aromatic systems for including at least one ring.For example, the C6-C30 virtues Base can be phenyl, naphthyl or tetralyl.At this point, at least one hydrogen atom of the aryl can use and on terms above The identical substituent that " substitution " limits replaces.
C6-C30 aryloxy group used herein can be phenoxy group.At this point, at least one hydrogen of the aryloxy group is former Son is available to be replaced with the identical substituent that terms above " substitution " limits.
C2-C30 heteroaryls used herein refer to include at least one hetero atom selected from N, O, P and S and remaining is former Son is the organic group of carbon.For example, the C2-C30 heteroaryls can be pyridine radicals.At this point, at least the one of the heteroaryl A hydrogen atom can use to be replaced with the identical substituent that terms above " substitution " limits.
The additive can be represented by following formula 2：
<Formula 2>
Wherein A1And A2It is each independentlyCondition is A1With A2IncludingIt is at least one；
B3And B4Be each independently singly-bound,Or C1-C5 alkylidenes；With
R’1、R’2、R”1、R”2、R”3And R "4It is each independently hydrogen, halogen group, hydroxyl, cyano group ,-C (=O) Ra、-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa,-S (=O) Ra,-S (=O)2Ra、-P(Ra)2, it is substituted or unsubstituted It is C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxies, substituted or unsubstituted C2-C20 alkenyls, substituted or unsubstituted C2-C20 alkynyls, C2-C20 oxyalkylene groups, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 virtues Base, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryls or its combination, wherein RaFor hydrogen, C1-C10 alkyl or C6-C20 aryl,
Wherein R '1、R’2、R”1、R”2、R”3And R "4It is at least one including polar functional group chosen from the followings：Halogen radical Group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa、-P(Ra)2, it is substituted or unsubstituted C1-C20 alkoxies, C2-C20 oxyalkylene groups, substituted or unsubstituted C6-C30 aryloxy group and substituted or unsubstituted C2- C30 heteroaryls.
The substituent used in formula 2 is identical with being limited in formula 1.
The additive of the formula 2 may be based on the compound of benzothiazole.The example bag of the compound based on benzothiazole Include the compound based on indazole, the compound based on benzimidazole and the compound based on benzotriazole.
The additive of the formula 2 includes possessing the polar functional group with non-covalent electron pair of electron donation and miscellaneous The nitrogen-atoms with non-covalent electron pair in ring, and therefore there is the core part for the oxidation potential for possessing reduction.Therefore, non-aqueous By before oxidation on the surface of cathode, the additive is aoxidized organic solvent, and so as to form film in a short time.
For example, the additive can be at least one chosen from the followings： For example, the additive can be selected from as follows At least one： For example, the additive can be at least one chosen from the followings：
The amount of the additive can be based in the range of about 10 weight %, e.g., from about 0.01-5 weight % of about 0.005- The gross weight of the electrolyte.
If the amount of the additive is within the above range, the additive dissolves (decompose) in the electrolyte, makes Obtain and thin biography is formed with the side reaction of the wherein described electrolyte state that hardly (seldom, little) occurs on positive electrode surface Guided membrane, thus can improve the cycle life characteristics of lithium secondary battery.
The lithium salts can be such as LiPF6、LiBF4、LiSbF6、LiAsF6、LiCF3SO3、LiN(CF3SO2)3、Li (CF3SO2)2N、LiC4F9SO3、LiClO4、LiAlO2、LiAlCl4, LiN (C that wherein x and y are natural numberxF2x+1SO2)(CyF2y+ 1SO2), LiCl, LiI, di-oxalate lithium borate or its combination.
It is described for the electrolyte of lithium secondary battery in the lithium salts dissolving that uses in organic solvent and be used as lithium ion Source, so that the operation of lithium secondary battery can be carried out, and promotes the migration of lithium ion between a positive electrode and a negative electrode.The lithium Salt can be any of the material that is commercially used in lithium battery.
The lithium salts also acts as supporting electrolyte salt.
The concentration of the lithium salts can be in the art in usually used concentration range.For example, the institute in the electrolyte The concentration for stating lithium salts can be in the range of about 0.1- about 2.0M.If the concentration of the lithium salts is within the above range, can be suitably The concentration of the electrolyte is kept to improve the performance of the electrolyte and can suitably keep the viscosity of the electrolyte to change The mobility of kind lithium ion.
The example of the non-aqueous organic solvent include the solvent based on carbonic ester, the solvent based on ester, the solvent based on ether, Solvent based on ketone, the solvent based on alcohol, aprotic solvent, and combinations thereof.
The non-aqueous organic solvent that the electrolyte includes can as the ion of electrochemical reaction for participating in battery Migrate across its medium.The non-aqueous organic solvent can be any of a variety of materials that is used commercially in this area.
The example of the solvent based on carbonic ester includes dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonic acid two Propyl ester (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonic acid ester (EPC), methyl ethyl carbonate (MEC), ethylene carbonate (EC), carbonic acid Sub- propyl ester (PC) and butylene carbonate (BC).The example of the solvent based on ester includes methyl acetate, ethyl acetate, acetic acid N-propyl, tert-butyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, decalactone, valerolactone, mevalonolactone and oneself Lactone.The example of the solvent based on ether include butyl oxide, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethoxy-ethane, 2- methyltetrahydrofurans and tetrahydrofuran.The example of the solvent based on ketone includes cyclohexanone.
The example of the solvent based on alcohol includes ethanol and isopropanol.The example of the aprotic solvent includes：By R- The nitrile that CN is represented, wherein R is the straight chain with 2-20 carbon atom, side chain or cricoid alkyl, and R can be with double bond, aromatic ring Or ehter bond；Acid amides such as dimethylformamide；Dioxolanes such as 1,3- dioxolanes；And sulfolane.
The non-aqueous organic solvent can be used alone or can be combined using its at least two.If it is applied in combination at least two Non-aqueous organic solvent, mixed volume ratio can suitably adjust and general for this area according to the expected performance of battery to be manufactured Logical technical staff can be apparent.
If moreover, using the solvent based on carbonic ester, it can be combined and use cyclic carbonate and linear carbonate.This In the case of, the volume ratio of the cyclic carbonate and linear carbonate can be about 1:1- about 1:In the range of 9.If the ring-type The volume ratio of carbonic ester and linear carbonate within the range, including the solvent based on carbonic ester electrolyte have it is good Performance.
In addition to the solvent based on carbonic ester, the non-aqueous organic solvent can further comprise based on aromatic hydrocarbon (aromatic hydrocarbons) organic solvent.At this point, the solvent based on carbonic ester can be with the organic solvent based on aromatic hydrocarbon With about 1:1- about 30:1 volume ratio mixing.
The organic solvent based on aromatic hydrocarbon can be the compound based on aromatic hydrocarbon represented by following formula 3：
<Formula 3>
Wherein Ra-RfIt is each independently hydrogen, halogen atom, C1-C10 alkyl, haloalkyl or its combination.
The example of the organic solvent based on aromatic hydrocarbon includes benzene, fluorobenzene, 1,2- difluoro-benzenes, bis- fluoro of 1,3- Benzene, 1,4- difluoro-benzenes, 1,2,3- trifluoro-benzenes, 1,2,4- trifluoro-benzenes, chlorobenzene, 1,2- dichlorobenzenes, 1,3- dichloro-s Benzene, 1,4- dichlorobenzenes, 1,2,3- trichloro-benzenes, 1,2,4- trichloro-benzenes, iodobenzene, 1,2- diiodo-benzenes, bis- iodos of 1,3- Benzene, 1,4- diiodo-benzenes, 1,2,3- phenyl triiodides, 1,2,4- phenyl triiodides, toluene, fluorotoluene, bis- fluorotoluenes of 2,3-, 2, Bis- fluorotoluenes of 4-, bis- fluorotoluenes of 2,5-, tri- fluorotoluenes of 2,3,4-, tri- fluorotoluenes of 2,3,5-, chlorotoluene, 2,3- bis- Chlorotoluene, 2,4- dichloro-s toluene, 2,5- dichloro-s toluene, tri- chlorotoluenes of 2,3,4-, tri- chlorotoluenes of 2,3,5-, iodo Toluene, bis- iodo toluene of 2,3-, bis- iodo toluene of 2,4-, bis- iodo toluene of 2,5-, tri- iodo toluene of 2,3,4-, 2,3,5- triiodos For toluene, dimethylbenzene, and combinations thereof.
It will be described in including above-mentioned lithium secondary battery of electrolyte now.
Another embodiment according to the present invention, lithium secondary battery include：Cathode, it include Lithium-ion embeding wherein or from The wherein positive active material of deintercalation；Anode, it includes Lithium-ion embeding wherein or the negative electrode active material from wherein deintercalation；With And the electrolyte between the cathode and anode, wherein the electrolyte includes lithium salts, non-aqueous organic solvent and by following formula 1 The additive of expression：
<Formula 1>
Wherein A1-A9It is each independentlyCondition is A1-A9Bag IncludeIt is at least one；
CY1 is C3-C6 aromatic rings, and CY2 is C2-C5 aromatics or non-aromatic ring；
B1And B2Be each independently singly-bound,Or C1-C5 alkylidenes；With
R1And R2It is each independently hydrogen, halogen group, cyano group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa,-S (=O) Ra,-S (=O)2Ra、-P(Ra)2, substituted or unsubstituted C1-C20 alkyl, substitution or Unsubstituted C1-C20 alkoxies, substituted or unsubstituted C2-C20 alkenyls, substituted or unsubstituted C2-C20 alkynyls, C2-C20 It is oxyalkylene group, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryls or its combination, wherein RaFor hydrogen, C1-C10 alkyl or C6- C20 aryl,
Condition is R1And R2It is at least one including polar functional group chosen from the followings：Halogen group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa、-P(Ra)2, substituted or unsubstituted C1-C20 alkoxies, C2-C20 oxyalkylene groups, substituted or unsubstituted C6-C30 aryloxy group and substituted or unsubstituted C2-C30 heteroaryls.
The additive of the formula 1 can be compound based on benzothiazole with polar functional group or derivatives thereof.It is described The example of compound based on benzothiazole includes the compound based on indazole, the compound based on benzimidazole and based on benzo The compound of triazole.
Before the non-aqueous organic solvent is by oxidation, the additive of the formula 1 is aoxidized, because it is with more non-than described The low oxidation potential of aqueous organic solvent, thus forms film on the surface of cathode.It is therefore possible to prevent powered on the surface of the cathode Solve the oxidation of matter.
In addition, the additive of the formula 1 includes the polar functional group with non-covalent electron pair for possessing electron donation With the nitrogen-atoms with non-covalent electron pair in heterocycle, and therefore have possess reduction oxidation potential core part, thus Form film.Moreover, the additive of the formula 1 can provide for smoothly migrating the passage of the lithium ion of the electrolyte, by This can obtain the lithium secondary battery with improved life characteristic.
It is formed in the film on positive electrode surface and suppresses other electrolyte side reaction and the elution of metal ion, or even Battery is also in this way, thus contributing improved High temperature storage characteristic and life characteristic when being exposed to high temperature.
When the battery with improved life characteristics at high temperature is used in electric car, the battery make it that the electric car can Harsh environment is resistant to, and the improvement of High temperature storage characteristic is so that the battery for including the electrolyte is more suitable for being likely to be exposed at height The electric power storage application of temperature.
The additive can be represented by following formula 2：
<Formula 2>
Wherein A1And A2It is each independentlyCondition is A1With A2IncludingIt is at least one；
B3And B4Be each independently singly-bound,Or C1-C5 alkylidenes；With
R’1、R’2、R”1、R”2、R”3And R "4It is each independently hydrogen, halogen group, hydroxyl, cyano group ,-C (=O) Ra、-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa,-S (=O) Ra,-S (=O)2Ra、-P(Ra)2, it is substituted or unsubstituted It is C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxies, substituted or unsubstituted C2-C20 alkenyls, substituted or unsubstituted C2-C20 alkynyls, C2-C20 oxyalkylene groups, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 virtues Base, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C2-C30 heteroaryls or its combination, wherein RaFor hydrogen, C1-C10 alkyl or C6-C20 aryl,
Condition is R '1、R’2、R”1、R”2、R”3And R "4It is at least one including polar functional group chosen from the followings：Halogen radical Group, hydroxyl ,-C (=O) Ra,-C (=O) ORa,-OC (=O) ORa,-CH=N (Ra)、-SRa、-P(Ra)2, it is substituted or unsubstituted C1-C20 alkoxies, C2-C20 oxyalkylene groups, substituted or unsubstituted C6-C30 aryloxy group and substituted or unsubstituted C2- C30 heteroaryls.
The substituent used in formula 2 is identical with being limited in formula 1.
The additive of the formula 2 may be based on the compound of benzothiazole.The example bag of the compound based on benzothiazole Include the compound based on indazole, the compound based on benzimidazole and the compound based on benzotriazole.
The additive of the formula 2 includes possessing the polar functional group with non-covalent electron pair of electron donation and miscellaneous The nitrogen-atoms with non-covalent electron pair in ring, and therefore, before non-aqueous organic solvent is on positive electrode surface by oxidation, institute State additive to be aoxidized, thus form film in a short time.Therefore, the secondary electricity of lithium of the electrolyte comprising the additive is included Pond can have improved life characteristics at high temperature and High temperature storage characteristic.
For example, the additive can be at least one chosen from the followings： For example, the additive can be selected from as follows At least one： For example, the additive can be at least one chosen from the followings：
Another embodiment according to the present invention, lithium secondary battery includes cathode, anode and electrolyte, wherein the electrolysis Matter includes lithium salts, non-aqueous organic solvent and the additive represented by equation 1 above, and the cathode includes what is formed in its surface Film, wherein the membrane part or fully derive from the electrolyte the additive.
Therefore, even if when the lithium secondary battery charges under high voltage (being greater than 4.3V), the secondary electricity of lithium Pond also has excellent capacity maintenance characteristics.In addition, the lithium secondary battery has excellent life characteristic and excellent capacity Preservation characteristics.
The thickness of the film can be about 0.5nm- about 100nm, e.g., from about 0.5nm- about 80nm's, e.g., from about 0.5nm-50nm In the range of.
When the film being formed on the positive electrode surface of the lithium secondary battery thickness within the above range when, the film It can not adversely influence the migration of lithium ion and can effectively prevent the oxidation of the electrolyte on positive electrode surface.
The amount of the additive can be based in the range of about 10 weight %, e.g., from about 0.01-5 weight % of about 0.005- The gross weight of the electrolyte.
If the amount of the additive is within the above range, the additive dissolving is in the electrolyte so that can be in cathode The state hardly occurred with the side reaction of wherein described electrolyte on surface forms thin conducting film, and it is secondary thus can to improve lithium The cycle life characteristics of battery.
Fig. 3 is the decomposition diagram of lithium secondary battery 100 according to embodiment.The lithium secondary battery of Fig. 3 is cylinder , but the shape not limited to this of the lithium secondary battery.For example, the lithium secondary battery can have rectangular shape or pouch-shaped Shape.
Lithium secondary battery can be divided into lithium ion battery, lithium ion polymer battery or lighium polymer according to partition plate and electrolyte Battery；Cylindrical battery, rectangular battery, Coin-shaped battery or pouch-type battery can be divided into according to the shape of battery；With can be according to electricity The size in pond is divided into block (bulk) type battery or membrane-type cell.The type of the lithium secondary battery of embodiment does not have according to the present invention Limitation.The structure and preparation method of above-mentioned battery are known in the art, and are therefore not described in detail herein.
With reference to figure 3, lithium secondary battery 100 is cylindrical, and mainly includes anode 112, cathode 114, between anode 112 Partition plate 113 between cathode 114, impregnates the electrolyte (not shown) of anode 112, cathode 114 and partition plate 113, battery with it Container 120, and for encapsulating the package parts 140 of battery case 120.Anode 112, partition plate 113 and cathode 114 sequentially accumulate and Then wind, the structure of winding is placed in battery case 120 in a spiral form then, thus manufacture lithium secondary battery 100.
Anode 112 includes collector and the negative electrode active material layer being formed on the collector, wherein the anode is lived Property material layer includes negative electrode active material.
As the collector for anode, according to voltage range, copper, nickel or SUS collectors can be used.For example, it can be used Copper current collector is as the collector for anode.
The negative electrode active material can be any material usually used in the art.For example, the negative electrode active material The example of matter include lithium metal, can with the metal material of lithium alloyage, transition metal oxide, for adulterating or going elements doped lithium Material and for reversibly embedded or deintercalate lithium ions material.
The example of the transition metal oxide includes barium oxide, lithium-barium oxide etc..It is described to adulterate or go to mix The example of the material of miscellaneous lithium includes：Si；SiOx(0<x<2)；Si-Y alloys, wherein Y are alkali metal, alkaline-earth metal, 13-16 races member Element, transition metal, rare earth element or its combination, and be not Si；Sn；SnO2；With Sn-Y alloys, wherein Y is alkali metal, alkaline earth Metal, 13-16 races element, transition metal, rare earth element, and combinations thereof, and be not Sn.Moreover, described can adulterate or go to mix At least one of the material of miscellaneous lithium can be with SiO2It is applied in combination.Element Y can be Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf、V、Nb、Ta、Db、Cr、Mo、W、Sg、Tc、Re、Bh、Fe、Pb、Ru、Os、Hs、Rh、Ir、Pd、Pt、Cu、Ag、Au、Zn、Cd、 B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po or its combination.
It is described to be reversibly embedded in or the material of deintercalate lithium ions can be carbonaceous material and usual in the lithium secondary battery The various carbonaceous negative electrode active materials used it is any.It is described to be reversibly embedded in or the example of the material of deintercalate lithium ions Including crystalline carbon, amorphous carbon and its combination.The example of the crystalline carbon includes native graphite and Delanium, it each has There are unsetting (shapeless) shape, plate shape, chip shape, spherical shape or fiber shape.The example bag of the amorphous carbon Include soft carbon (low temperature calcination carbon), hard carbon, mesophase pitch carbonized product and calcined coke.
The negative electrode active material layer may also include adhesive, and further can optionally include conductive agent.
Described adhesive may be allowed that anode active material particles are adhering to each other and the negative electrode active material is adhered to institute State collector.The example of described adhesive includes, but not limited to polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, two Acetylcellulose, polyvinyl chloride, carboxylation polyvinyl chloride, polyvinyl fluoride, polymer, the polyvinylpyrrolidone of the oxygen containing ethylidene Ketone, polyurethane, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, butadiene-styrene rubber, acroleic acid esterification butadiene-styrene rubber, Epoxy resin and nylon.
The conductive agent provides electric conductivity to electrode, and can be not cause any chemical change in lithium secondary battery 100 And it is any of a variety of materials of electronic conduction.For example, the conductive agent can be native graphite, and Delanium, carbon black, acetylene It is black, Ketjen black, carbon fiber, and copper, nickel, the metal dust or fiber of aluminium or silver.Spread out moreover, can be combined using such as polyphenylene The conductive material of biology.The example of the collector includes copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, foam copper, coating Have conducting metal polymeric substrates, and combinations thereof.
The amount of the negative electrode active material, adhesive and conductive agent can be commercially used for it is identical in lithium secondary battery Horizontal use.For example, the negative electrode active material is verified, the mixed weight ratio of the sum of the conductive agent and adhesive can be about 98: 2- about 92:In the range of 8, and the mixed weight of the conductive agent and adhesive ratio can be about 1:1.5- about 1:In the range of 3.But It is that the ratio is not limited to above example.
Cathode 114 includes collector and the positive electrode active material layer being formed on the collector.
The collector can be formed by Al, but for forming the material not limited to this of the collector.
The positive active material can be any of a variety of materials usually used in this field.For example, the cathode Active material can be that can reversibly be embedded in and the compound of deintercalate lithium ions.The positive active material may include lithium with being selected from One or more composite oxides of the metal of cobalt, manganese, nickel and combinations thereof.For example, the positive active material can be by following formula Any one represent compound：LiaA1-bBbD2, wherein 0.90≤a≤1.8 and 0≤b≤0.5；LiaE1-bBbO2-cDc, wherein 0.90≤a≤1.8,0≤b≤0.5 and 0≤c≤0.05；LiE2-bBbO4-cDc, wherein 0≤b≤0.5 and 0≤c≤0.05； LiaNi1-b-cCobBcDα, wherein 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05 and 0<α≤2；LiaNi1-b-cCobBcO2-α Fα, wherein 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05 and 0<α<2；LiaNi1-b-cCobBcO2-αF2, wherein 0.90≤a ≤ 1.8,0≤b≤0.5,0≤c≤0.05 and 0<α<2；LiaNi1-b-cMnbBcDα, wherein 0.90≤a≤1.8,0≤b≤0.5,0 ≤ c≤0.05 and 0<α≤2；LiaNi1-b-cMnbBcO2-αFα, wherein 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05 and 0< α<2；LiaNi1-b-cMnbBcO2-αF2, wherein 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05 and 0<α<2； LiaNibEcGdO2, wherein 0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5 and 0.001≤d≤0.1； LiaNibCocMndGeO2, wherein 0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5 and 0.001≤e≤0.1； LiaNiGbO2, wherein 0.90≤a≤1.8 and 0.001≤b≤0.1；LiaCoGbO2, wherein 0.90≤a≤1.8 and 0.001≤b ≤0.1；LiaMnGbO2, wherein 0.90≤a≤1.8 and 0.001≤b≤0.1；LiaMn2GbO4, wherein 0.90≤a≤1.8 Hes 0.001≤b≤0.1；QO2；QS2；LiQS2；V2O5；LiV2O5；LiIO2；LiNiVO4；Li(3-f)J2(PO4)3, wherein 0≤f≤2； Li(3-f)Fe2(PO4)3, wherein 0≤f≤2；And LiFePO4。
The example of the positive active material includes LiCoO2, wherein 0≤x<1 LiNi1-xCoxO2、Li1-xMxO2(M Mn Or Fe, 0.03<x<0.1)、Li[NixCo1-2xMnx]O2(0<x<0.5), wherein 0<Li [the Ni of x≤0.5xMnx]O2、Li1+x (M)1-yOz(0<X≤1,0≤y<1,2≤z≤4, M are transition metal), LiM2O4(M Ti, V or Mn), LiMxMn2-xO4(M was Cross metal and 0<x≤1)、LiFePO4、LiMPO4(M Mn, Co or Ni), V2O5、V2O3、VO2(B)、V6O13、V4O9、V3O7、 Ag2V4O11、AgVO3、LiV3O5、δ-MnyV2O5(0<y≤1)、δ-NH4V4O10、Mn0.8V7O16、LiV3O8、CuxV2O5(0<x≤1)、 CrxV6O13(0<x≤1)、M2(XO4)3(M be transition metal, X S, P, As, Mo or W) and Li3M2(PO4)3(M Fe, V or Ti)。
Especially, the positive active material can be Li1+x(M)1-xO2, wherein 0.05≤x≤0.2 and M are transition metal. The example of the transition metal M includes, but not limited to Ni, Co, Mn, Fe and Ti.
Since lithium ion is big to the weight ratio of the transition metal M in the positive active material, including The capacity of the lithium secondary battery of cathode comprising the positive active material can more improve.
In above formula, A Ni, Co, Mn or its combination；B for Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth element, Or its combination；D is O, F, S, P or its combination；E is Co, Mn or its combination；F is F, S, P or its combination；G for Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V or its combination；Q is Ti, Mo, Mn or its combination；I is Cr, V, Fe, Sc, Y or its combination；It is with J V, Cr, Mn, Co, Ni, Cu or its combination.
Above-claimed cpd can have clad on their surface.Alternatively, the compound can be with the change comprising clad Compound is applied in combination.The compound that the clad may include to coat element is as coated the oxide of element, coating the hydrogen of element Oxide, the oxyhydroxide for coating element, the carbonic acid oxonium salt for coating element or the hydroxyl carbonate for coating element.The bag The compound for covering element can be unbodied or crystallization.The cladding element that the clad includes can be Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr or its mixture.Can be by using the physical property to positive active material The various methods (such as spraying or dipping) not adversely affected it is any by using the cladding member with above-claimed cpd Element forms clad.The clad forming method can be apparent for those skilled in the art, and therefore be not described in detail.
The positive electrode active material layer can further comprise adhesive and conductive agent.
The operating potential of the positive active material can be 4.5V ± 0.5V, such as 4.5V ± 0.3V.
Described adhesive may be allowed that positive active material particle is adhering to each other and the positive active material adheres to institute State collector.The example of described adhesive includes, but not limited to polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, two Acetylcellulose, polyvinyl chloride, carboxylation polyvinyl chloride, polyvinyl fluoride, polymer, the polyvinylpyrrolidone of the oxygen containing ethylidene Ketone, polyurethane, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, butadiene-styrene rubber, acroleic acid esterification butadiene-styrene rubber, Epoxy resin and nylon.
The conductive agent provides electric conductivity to electrode, and can be not cause any chemical change in lithium secondary battery 100 And it is any of a variety of materials of electronic conduction.For example, the conductive agent can be native graphite, and Delanium, carbon black, acetylene It is black, Ketjen black, carbon fiber, Huo Zhetong, nickel, the metal dust or fiber of aluminium or silver.Moreover, such as polypheny lene derivatives are led Electric material can be used alone or is applied in combination with least two of the conductive material.
The amount of the positive active material, adhesive and conductive agent can be commercially used for it is identical in lithium secondary battery Horizontal use.For example, the positive electrode active material is verified, the mixed weight ratio of the sum of the conductive agent and adhesive can be about 98: 2- about 92:In the range of 8, and the mixed weight of the conductive agent and adhesive ratio can be about 1:1.5- about 1:In the range of 3.But It is that the mixed weight ratio can be not limited to above example.
In order to form electrode such as anode 112 and cathode 114, active material, adhesive and conductive agent are mixed in a solvent To prepare active compound composition, and the active compound composition is applied on a current collector.The electrode manufacturing method is this Known to field, and therefore it is not described in detail herein.The solvent can be 1-methyl-2-pyrrolidinone, but not limited to this.
According to the type of lithium secondary battery, partition plate can be between anode and cathode.The partition plate can be polyethylene, poly- third The individual layer of alkene or Kynoar, or at least two multilayer of these materials.Moreover, the partition plate can be mixing multilayer such as Polyethylene/polypropylene layer, polyethylene/polypropylene/polyethylene layer or polypropylene, polyethylene/polypropylene layer.
One or more embodiments are described in further detail referring now to following embodiments.These embodiments are only used for The purpose of explanation, and it is not intended to limit the scope of one or more of embodiments.
In addition, the detailed description of technical characteristic known to persons of ordinary skill in the art is not provided herein.
[embodiment]
Embodiment 1：Preparation for the electrolyte of lithium secondary battery
Electrolyte for lithium secondary battery is prepared by the following procedure：Represented using 0.1 weight % as additive by following formula 4 LiPF as lithium salts of 5- hydroxy indazoles and 1.3M6It is added to the ethylene carbonate including 30 volume %, the carbon of 50 volume % In the mixed organic solvents of the methyl ethyl carbonate of diethyl phthalate and 20 volume %.
<Formula 4>
Embodiment 2：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 5- hydroxy indazoles of formula 4 are replaced as additive by the 3- indazole quinoline ketone (3-indazolinone) that following formula 5 represents.
<Formula 5>
Embodiment 3：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s 2- (methylsulfany) benzimidazoles represented by following formula 6 replace the 5- hydroxy indazoles of formula 4 as additive.
<Formula 6>
Embodiment 4：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s 2- (2- pyridine radicals) benzimidazoles represented by following formula 7 replace the 5- hydroxy indazoles of formula 4 as additive.
<Formula 7>
Embodiment 5：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 5- hydroxy indazoles of formula 4 are replaced as additive by the 4- hydroxyl -1H- benzotriazole that following formula 8 represents.
<Formula 8>
Embodiment 6：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 1,1 '-trimethylene double (benzotriazole) represented by following formula 9 replaces the 5- hydroxy indazoles of formula 4 as additive.
<Formula 9>
Comparative example 1：Preparation for the electrolyte of lithium secondary battery
Electrolyte for lithium secondary battery is prepared by the following procedure：LiPF using 1.3M as lithium salts6It is added to including 30 The mixed organic solvents of the methyl ethyl carbonate of the ethylene carbonate of volume %, the diethyl carbonate of 50 volume % and 20 volume % In, and without using additive.
Comparative example 2：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 5- hydroxy indazoles of formula 4 are replaced as additive by the indenes that following formula 10 represents.
<Formula 10>
Comparative example 3：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 5- hydroxy indazoles of formula 4 are replaced as additive by the indazole that following formula 11 represents.
<Formula 11>
Comparative example 4：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 5- hydroxy indazoles of formula 4 are replaced as additive by the benzimidazole that following formula 12 represents.
<Formula 12>
Comparative example 5：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 5- hydroxy indazoles of formula 4 are replaced as additive by the 2- tolimidazoles that following formula 13 represents.
<Formula 13>
Comparative example 6：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 5- hydroxy indazoles of formula 4 are replaced as additive by the 1H- benzotriazole that following formula 14 represents.
<Formula 14>
Comparative example 7：Preparation for the electrolyte of lithium secondary battery
The electrolyte for lithium secondary battery is prepared in the same manner as in example 1, except using 0.1 weight %'s The 5- hydroxy indazoles of formula 4 are replaced as additive by the 5- methylbenzotrazoles that following formula 15 represents.
<Formula 15>
Embodiment 7：The manufacture of lithium secondary battery
By Li as a positive electrode active material1.10Ni0.23Co0.23Mn0.43O2Powder, by by 5 weight % Kynoar (PVdF) adhesive prepared in 1-methyl-2-pyrrolidinone (NMP) and conductive agent (Denka black) are dissolved in 92:4:4 Weight ratio is added in agate mortar and mixes to prepare slurry.Applied by rod and the slurry is coated in the aluminium with 15 μ m thicks On paper tinsel.By products therefrom be placed in 90 DEG C of baking oven and it is dry about 2 it is small when to evaporate NMP, be subsequently placed in the vacuum at 120 DEG C In baking oven and it is dry about 2 it is small when with evaporating completely NMP.Then, products therefrom compacting and punching (punch) are had 60 to obtain The cathode for coin unit battery of μ m thick.
Using the cathode with 1.5cm diameters, the graphite cathode with 1.6cm diameters, polyethylene separator and according to Electrolyte for lithium secondary battery prepared by embodiment 1 manufactures lithium secondary battery.
Embodiment 8：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to embodiment 2 Matter.
Embodiment 9：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to embodiment 3 Matter.
Embodiment 10：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to embodiment 4 Matter.
Embodiment 11：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to embodiment 5 Matter.
Embodiment 12：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to embodiment 6 Matter.
Comparative example 8：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to comparative example 1 Matter.
Comparative example 9：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to comparative example 2 Matter.
Comparative example 10：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to comparative example 3 Matter.
Comparative example 11：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to comparative example 4 Matter.
Comparative example 12：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to comparative example 5 Matter.
Comparative example 13：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to comparative example 6 Matter.
Comparative example 14：The manufacture of lithium secondary battery
Lithium secondary battery is manufactured in a manner of in the same manner as in Example 7, except using the electrolysis prepared according to comparative example 7 Matter.
(element cell performance test)
Evaluate embodiment 1：The evaluation of lithium-ion-conducting (lithium ionic conductivity)
The lithium secondary battery manufactured according to embodiment 7 and 10 and comparative example 8 undergoes the charging for chemical conversion at room temperature With electric discharge twice.In formation process, the lithium secondary battery with the constant current charge of 0.2C until voltage reaches 4.4V, so Charge afterwards under the constant voltage of 4.4V until electric current reaches 0.05C.Then, discharged with the constant current of 0.2C until electricity Pressure reaches 2.8V.The lithium secondary battery method described above that experienced charging and discharging for chemical conversion is filled with the electric current of 0.5C Electricity, is then disassembled.Then, by using XPS (Physical Electronics Quantom 2000) on positive electrode surface The film of formation is evaluated to confirm whether its lithium-ion-conducting improves, and the results are shown in Fig. 2.
As shown in Figure 2, in 684eV to the peak that LiF (it is non-conducting for lithium ion) is observed between 686eV.
Included by using the film formed on each comfortable positive electrode surface of the electrolyte in embodiment 7 and 10 than by using right The LiF of the few amount of film that electrolyte in ratio 8 is formed on positive electrode surface.
By the result, it was demonstrated that the film formed by using the electrolyte including embodiment 7 and 10 on positive electrode surface is had There is improved lithium-ion-conducting.
Evaluate embodiment 2-1：The life characteristics at high temperature 1 of lithium secondary battery
Undergo the charging for chemical conversion at room temperature according to the embodiment 7-10 and comparative example 8-12 lithium secondary batteries manufactured With electric discharge twice.In formation process, the lithium secondary battery with the constant current charge of 0.2C until voltage reaches 4.4V, so Charge afterwards under the constant voltage of 4.4V until electric current reaches 0.05C.Then, discharged with the constant current of 0.2C until electricity Pressure reaches 2.8V.The lithium secondary battery method described above that experienced charging and discharging for chemical conversion is filled with the electric current of 0.5C Electricity, then discharges under the electric current of 0.2C until voltage reaches 2.8V.Charging and discharging condition in this case is used as reference Charging and discharging condition, and discharge capacity in this case is used as reference capacity.
Then, in order to evaluate life characteristics at high temperature, by the lithium secondary battery in 45 DEG C of thermostatic chamber method described above Charged with the electric current of 1C, then with the current discharge of 1C until voltage reaches 2.8V.Then, measurement discharge capacity (is followed at the 1st time The discharge capacity of ring).Charging and discharging process is repeated to evaluate cycle life.The lithium secondary battery is measured in each circulation Discharge capacity and its 100th time circulation discharge capacity, and by its calculate capacity retention ratio.Calculated using Equation 1 below Capacity retention ratio (%)：
[equation 1]
Capacity retention ratio (%)=[discharge capacity circulated at the 100th time/in the discharge capacity of the 1st circulation] × 100
The capacity retention ratio being computed as described above is shown in table 1 below and Fig. 4 A.
<Table 1>
Evaluate embodiment 2-2：The life characteristics at high temperature 2 of lithium secondary battery
The lithium secondary battery manufactured according to embodiment 11 and 12 and comparative example 8,13 and 14 is with evaluating in embodiment 2-1 Identical mode undergo at room temperature for chemical conversion charging and discharging twice.
Then, in order to evaluate life characteristics at high temperature, by the lithium secondary battery in 60 DEG C of thermostatic chamber method described above Charged with the electric current of 1C, then with the current discharge of 1C until voltage reaches 2.8V.Then, measurement discharge capacity (is followed at the 1st time The discharge capacity of ring).Charging and discharging process is repeated to evaluate cycle life.The lithium secondary battery is measured in each circulation Discharge capacity and its 100th time circulation discharge capacity, and by its calculate capacity retention ratio.Calculated using above equation 1 Capacity retention ratio (%).
The capacity retention ratio being computed as described above is shown in table 2 below and Fig. 4 B.
<Table 2>
Reference table 1 and Fig. 4 A, do not include additive or including without polar functional with what is manufactured according to comparative example 8-12 The lithium secondary battery of additive of group is compared, according to embodiment 7-10 manufacture include with polar functional group based on indazole Additive or capacity retention ratio of the lithium secondary battery of additive with improvement based on benzimidazole.Therefore, it was demonstrated that embodiment The lithium secondary battery of 7-10 has the high temperature service life longer than each lithium secondary battery of comparative example 8-12.
In addition, reference table 2 and Fig. 4 B, with comparative example 8,13 and 14 not including additive or including without polar functional The lithium secondary battery of the additive of group is compared, and embodiment 11 and 12 includes the adding based on benzotriazole with polar functional group Add the lithium secondary battery of agent there is improved capacity retention ratio.Therefore, it was demonstrated that the lithium secondary battery of embodiment 11 and 12 have than The high temperature service life of each lithium secondary battery length of comparative example 8,13 and 14.
Evaluate embodiment 3：The High temperature storage characteristic of lithium secondary battery
By undergone for chemical conversion charging and discharging process twice and reference be charged and discharged process 7 He of embodiment 10 and the lithium secondary battery of comparative example 8 charge in the case where reference is charged and discharged the charge condition of condition, and by the lithium two of charging Primary cell be maintained in 100 DEG C of thermostatic chamber about 40 it is small when.Then, by being kept at said high temperatures by each lithium secondary battery Before or after be connected to after charger and discharger and measure its voltage immediately and measure the open-circuit voltage of each lithium secondary battery (OCV) drop.In addition, the discharge capacity (discharge capacity after placing at said high temperatures) of the lithium secondary battery is obtained, and by It calculates its high temperature capacity retention ratio.Then, measure each lithium secondary battery and the discharge capacity circulated be charged and discharged at the 1st time, And its high temperature capacity restoration rate is calculated by it.
The high temperature capacity retention ratio, at said high temperatures place before or after OCV, the OCV between difference and High temperature capacity restoration rate is shown in table 3 below and 4 and illustrates in fig. 5-7.
The high temperature capacity retention ratio (%) and high temperature capacity restoration rate (%) are obtained by Equation 2 below and 3 respectively：
<Equation 2>
High temperature capacity retention ratio (%)=[discharge capacity/reference capacity after placing at high temperature] × 100
<Equation 3>
High temperature capacity restoration rate (%)=[discharge capacity that being charged and discharged at the 1st time after placing at high temperature is circulated/ Reference capacity] × 100
<Table 3>
<Table 4>
Reference table 3 and 4 and Fig. 5-7, placed at 100 DEG C about 40 it is small when embodiment 7 and 10 lithium secondary battery tool There is the high discharge capacity of the lithium secondary battery of the comparative example 8 than keeping under the same conditions, and therefore there is improved high temperature to hold OCV characteristics after measuring conservation rate and placing at high temperature.In addition, the lithium secondary battery of embodiment 7 and 10 is with high in high temperature Transfer the residual capacity postponed and therefore there is improved high temperature capacity restoration rate.
As described above, the one or more of embodiment of above according to the present invention, the electrolyte for lithium secondary battery Polarity film is formed on positive electrode surface, and therefore there is improved life characteristics at high temperature and High temperature storage characteristic.In addition, use The film formed by compound based on benzothiazole with polar functional group or derivatives thereof can be manufactured with improved lithium ion Conductive lithium secondary battery.
It is to be understood that the illustrative embodiments described in it should only consider in the sense that description and be not used in the mesh of limitation 's.The description of feature or aspect should be typically considered to can be used for other classes in other embodiments in various embodiments Like feature or aspect.

Claims (10)

1. lithium secondary battery, including：
Cathode, it includes Lithium-ion embeding wherein or the positive active material from its deintercalation；
Anode, it includes Lithium-ion embeding wherein or the negative electrode active material from its deintercalation；And
Electrolyte between the cathode and anode,
Wherein described electrolyte includes lithium salts, non-aqueous organic solvent and additive,
The additive is a kind of compound chosen from the followings：
Wherein described additive is the compound based on indazole,
Wherein described cathode includes forming film in its surface, wherein the membrane part or fully deriving from the electrolyte In the additive, and
Wherein described negative electrode active material is at least one material chosen from the followings：Graphite, soft carbon, hard carbon, mesophase pitch carbon Change product and calcined coke.
2. the lithium secondary battery of claim 1, wherein the additive is at least one compound chosen from the followings：
3. the lithium secondary battery of claim 1, wherein the amount of the additive is in the range of about 10 weight % of about 0.005-, base In the gross weight of the electrolyte.
4. the lithium secondary battery of claim 1, wherein the amount of the additive is based in the range of about 5 weight % of about 0.01- The gross weight of the electrolyte.
5. the lithium secondary battery of claim 1, wherein the lithium salts is a kind of compound chosen from the followings：LiPF6、LiBF4、 LiSbF6、LiAsF6、LiCF3SO3、Li(CF3SO2)3C、Li(CF3SO2)2N、LiC4F9SO3、LiClO4、LiAlO2、LiAlCl4、 LiBPh4, LiN (C that wherein x and y are natural numberxF2x+1SO2)(CyF2y+1SO2), LiCl, LiI, di-oxalate lithium borate (LIBOB), and combinations thereof.
6. the lithium secondary battery of claim 1, wherein the non-aqueous organic solvent is the solvent based on carbonic ester, based on the molten of ester Agent, the solvent based on ether, the solvent based on ketone, the solvent based on alcohol, aprotic solvent or its combination.
7. the lithium secondary battery of claim 1, wherein the thickness of the film is in the range of about 0.5nm- about 100nm.
8. the lithium secondary battery of claim 1, wherein the positive active material is at least one material chosen from the followings： LiCoO2, wherein 0≤x<1 LiNi1-xCoxO2, wherein M is Mn or Fe and 0.03<x<0.1 Li1-xMxO2, wherein 0<x<0.5 Li [NixCo1-2xMnx]O2, wherein 0<Li [the Ni of x≤0.5xMnx]O2, wherein 0<x≤1、0≤y<1st, 2≤z≤4 and M was Cross the Li of metal1+x(M)1-yOz, wherein M is the LiM of Ti, V or Mn2O4, wherein M is the LiM of transition metalxMn2-xO4, LiFePO4, wherein M is the LiMPO of Mn, Co or Ni4, V2O5, V2O3, VO2(B), V6O13, V4O9, V3O7, Ag2V4O11, AgVO3, LiV3O5, δ-MnyV2O5, δ-NH4V4O10, Mn0.8V7O16, LiV3O8, CuxV2O5, CrxV6O13, wherein M be transition metal and X be S, P, the M of As, Mo or W2(XO4)3, and the Li that wherein M is Fe, V or Ti3M2(PO4)3。
9. the lithium secondary battery of claim 1, wherein the positive active material is Li1+x(M)1-xO2, wherein 0.05≤x≤0.2 It is transition metal with M.
10. the lithium secondary battery of claim 1, wherein the positive active material has the operating potential of 4.5V ± 0.5V.
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Application publication date: 20180420